CN113385141B - Facility CO for improving plant cultivation by applying ZSM-5 molecular sieve2Concentration and method of crop growth - Google Patents
Facility CO for improving plant cultivation by applying ZSM-5 molecular sieve2Concentration and method of crop growth Download PDFInfo
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Abstract
The invention discloses a method for improving CO content in plant cultivation facilities by applying a ZSM-5 molecular sieve2Method for concentration and crop growth based on ZSM-5 molecular sieve on CO2The adsorption and desorption of the organic carbon can realize the CO in the facility cultivation environment at normal temperature and normal pressure through regulating and controlling the pretreatment process, the application amount of the ZSM-5 molecular sieve and the like in the method2The concentration is enriched, the facility cultivation environment of the pretreated ZSM-5 molecular sieve is applied, the growth of crops is better, the stem thickness is increased, and the fresh weight is improved. In addition, the method is simple, convenient and safe to operate, environment-friendly and low in energy consumption, the ZSM-5 molecular sieve can be recycled, and the CO can still be stably treated after recycling2Adsorption and desorption capacity of (A) compared to other CO2Enrichment methods, such as a combustion gas making method, a chemical reaction method and the like, are more in line with the requirements of low-carbon agriculture.
Description
Technical Field
The invention belongs to the field of facility agriculture, and particularly relates to a facility CO improving plant cultivation by applying ZSM-5 molecular sieve2Concentration and method of crop growth.
Background
The facility agriculture in China develops rapidly, and plays an important role in the aspects of guaranteeing annual supply of agricultural products, increasing land productivity, promoting income increase of farmers and the like. However, due to the conditions of sealing and heat preservation in the cultivation facilities, CO in the room/shed is generated along with the photosynthesis of the crops2The concentration is continuously reduced, often only 100-200 ppm, and is far lower than CO of main facility crops such as solanaceous fruits and melons2The saturation point concentration is 1500ppm (Zhan Zhang, "study on developing low-carbon production technology for vegetables in facilities", Chinese vegetables, 2010(9):4-6), which severely limits the high quality and yield of crops. Increasing CO in facility environment in facility crop production2The concentration of the compound fertilizer can effectively improve the photosynthetic rate of plants, increase biomass, and enhance the resistance of the plants to adverse conditions such as high temperature, drought, salt stress and the like, thereby improving the yield and quality of crops and realizing the quality improvement and efficiency improvement of facility production.
CO is currently carried out in facilities2Enrichment (CO)2Fertilization) are the following main methods: ventilation, i.e. by window ventilation, but of CO2The concentration improving effect is limited, and the temperature in the greenhouse can be changed; CO 22Cylinder process, i.e. CO in high-pressure cylinders2The gasification is used, but the transportation is inconvenient; applying farmyard organic fertilizer, i.e. decomposing and fermenting compost and straw by microorganism to release CO2However, the operation is quite troublesome, and the risks of spreading diseases and insect pests and releasing toxic gas exist; gas-making by combustion, i.e. by combustion of natural gas or coal or like fuels to produce CO2However, a gas purification device needs to be additionally arranged, and fire hazard exists; chemical reaction, typically using the reaction of ammonium bicarbonate with dilute acid to produce CO2However, the method has the problems that the consumption of reaction raw materials is large, hazardous chemicals are difficult to purchase, the reaction rate is difficult to control, and the like, and ammonia gas which is harmful to the growth of plants is released. Among the above methods, a combustion gas production method and a chemical reaction method are commonly used, but both methods produce new CO2Does not meet the requirement of low-carbon agriculture, so that safe, simple, environment-friendly and efficient CO is developed2Enrichment technology is an urgent need of the current facility cultivation industry.
The zeolite molecular sieve is natural or artificial crystalAluminosilicate, with tunable internal cations, having the general formula: [ M2(I), M (II)]O·Al2O3·nSiO2·mH2And O. Zeolite molecular sieves have pores inside, and can sieve different fluid molecules according to the size of the effective pore diameter, and are commonly used for separation and purification of gas, liquid and the like. The zeolite molecular sieve has unique performance, the production cost is continuously reduced along with continuous innovation of a synthesis method, and the zeolite molecular sieve can be repeatedly used. At present, zeolite molecular sieves have been widely used in many fields such as chemical engineering, precision instruments, bioengineering, and environmental protection.
ZSM-5 type aluminosilicate molecular sieves are a typical representation of zeolitic molecular sieves. The ZSM-5 molecular sieve belongs to an orthorhombic system, the unit cell constant a is 2.01nm, b is 1.99nm, c is 1.34nm, and the unit cell composition is expressed as NanAlnSi96-nO192·16H2O, which has high hydrothermal stability and a pore diameter range of approximately 0.5-0.6 nm and can be realized in N through weak adsorption caused by interaction with a framework and strong adsorption caused by interaction with cations2/CO2、CO/CO2To CO in mixed gas2And (4) adsorption of molecules. ZSM-5 molecular sieve at 25 deg.C and 100 kPa for CO2And N2The amounts of adsorption of (A) were 1.355mmol/g and 0.169 mmol/g, respectively. (Hefti et al, "Adsorption equilibria of carbon dioxides and nitrogen on zeolites ZSM-5and 13X.", micropous and mesous Materials,2015,215: 215-. In addition, the ZSM-5 molecular sieve can also be improved to CO by adjusting the ratio of silicon to aluminum and the types of metal ions2Adsorption Performance (Wilson and Tezel, "CO2 and CO adsorption equilibrium on ZSM-5for different SiO2/Al2O3 ratios.”Separation Science and Technology,2019,54(5):722-730)。
Chinese patent publication No. CN108970590A discloses a method for capturing and enriching carbon dioxide in air by using an active material or a modified active material, and an application thereof, in which the active material and the modified active material are used to capture and enrich carbon dioxide in air, and the carbon dioxide is desorbed and used as a carbon dioxide fertilizer for microalgae cultivation, after long-term adsorption-desorption cycle use, the active material or the modified active material still maintains stable adsorption and desorption capacity for carbon dioxide, and the growth efficiency of microalgae treated by the method is significantly improved, but high-temperature heating is required during carbon dioxide desorption in the invention.
Disclosure of Invention
The invention provides a method for improving CO content in plant cultivation facilities by applying a ZSM-5 molecular sieve2The method for the concentration and the crop growth has simple operation and low energy consumption, and can meet the requirement of CO at normal temperature and normal pressure without adopting the modes of pressure change, heating and the like2Enriched facility cultivation environment application of CO2And the air fertilizer further promotes the growth of crops.
The technical scheme is as follows:
facility CO for improving plant cultivation by applying ZSM-5 molecular sieve2A method of concentration and crop growth comprising the steps of:
(1) pretreating the ZSM-5 molecular sieve to make the molecular sieve fully adsorb CO2；
(2) Transferring the pretreated ZSM-5 molecular sieve to CO2Facility cultivation environment with concentration less than or equal to 480ppm, ZSM-5 molecular sieve standing for slow release of CO2(ii) a CO improving facility cultivation environment2Concentration, promoting the growth of crops.
The invention is based on ZSM-5 molecular sieve to CO2The adsorption and desorption of the method develops a method for improving CO of plant cultivation facilities by applying ZSM-5 molecular sieve2The concentration and the crop growth method realize the CO in the facility cultivation environment by regulating and controlling the pretreatment process, the application amount of the ZSM-5 molecular sieve and the like in the method2The artificial regulation and control of the enrichment effect can meet the requirement of different crops and different growth periods of the crops on CO2Promoting the growth of crops.
In the step (1), the pretreatment mode is as follows: filling CO into the closed space filled with ZSM-5 molecular sieve2And sealing and standing for 0.1-12 h.
The ZSM-5 molecular sieve and CO2The volume ratio of the filling amount is 0.01-100: 1000.
Preferably, the adsorption saturation point, CO, of the ZSM-5 molecular sieve is taken into consideration2The utilization efficiency is the time cost, and the sealing and standing time is 1-4 h; the ZSM-5 molecular sieve and CO2The volume ratio of the filling amount is 0.1-4: 1000.
In the step (2), the dosage of the ZSM-5 molecular sieve is 30-100 cm per cubic meter of facility cultivation environment3。
In the step (2), the ZSM-5 molecular sieve stands to release CO slowly2And (4) taking out after at least 3h, returning to the step (1), and repeating for 1-10 times. After recycling for 1-10 times, the ZSM-5 molecular sieve is used for CO in the facility cultivation environment2The enriching effect of (A) is not obviously different from that of the first use.
Because of more water vapor in the facility cultivation environment, the ZSM-5 molecular sieve is dried and regenerated at high temperature for 3 times and then is continuously used, and the high-temperature drying and regeneration conditions are 100-300 ℃ and 1-48 hours.
Preferably, the crop is tomato.
Further preferably, in the step (1), the pretreatment method is: filling CO into the closed space filled with ZSM-5 molecular sieve2Sealing and standing for 1-4 h; the ZSM-5 molecular sieve and CO2The volume ratio of the filling amount is 1-4: 1000; in the step (2), the amount of the ZSM-5 molecular sieve is 40-90 cm per cubic meter of facility cultivation environment3. The ZSM-5 molecular sieve was pretreated under the above conditions and transferred to CO2Standing in tomato facility cultivation environment with concentration less than or equal to 480ppm for slow release of CO2After 1h, CO in facility cultivation environment2The concentration can be increased by 100-1000 ppm, and compared with a control group, the concentration of the intercellular CO of the leaves of the crops can be increased by 100-1000 ppm2The concentration is improved by 30-40%, the net photosynthetic rate is improved by 7-10%, and after 10 days of continuous application, the stem thickness growth amount of the crops is improved by 70-80%, and the fresh weight growth amount is improved by 55-70% compared with the control group.
Compared with the prior art, the invention has the following advantages:
the invention discloses a facility C for improving plant cultivation by applying ZSM-5 molecular sieveO2The method for the concentration and the crop growth is simple, convenient and safe to operate, environment-friendly and low in energy consumption, and in addition, the ZSM-5 molecular sieve can be recycled, and can still keep relatively stable CO after being recycled2Adsorption and desorption capacity of (a).
The invention can realize CO in the facility cultivation environment by regulating and controlling the pretreatment process, the application amount of the ZSM-5 molecular sieve and the like2Artificial regulation and control of enriching effect to meet the requirement of CO concentration for different crops and different growth periods in the cultivation process2The requirements of (a).
Drawings
FIG. 1 shows pretreatment, sealing and standing time versus ZSM-5 molecular sieve and a reference material CO2The effect of the enrichment effect.
FIG. 2 is a graph of the number of reuses versus the ZSM-5 molecular sieve and the control material CO2The effect of enrichment.
FIG. 3 is a graph of pretreated ZSM-5 molecular sieve and pretreated control material versus CO in a facility cultivation environment2The effect of concentration.
FIG. 4 shows the application of pretreated ZSM-5 molecular sieves and pretreated control material to 'Condition Red' tomato seedling intercellular CO in a facility cultivation environment2Influence of concentration and Net photosynthetic Rate, A is intercellular CO for 'Condition Red' tomato seedlings2The influence of concentration, B is the influence on the net photosynthetic rate of 'conditioner Red' tomato seedlings; a. b represents significant differences at the 5% level between the different treatments.
FIG. 5 is a graph of the change in the ` Condine Red ` tomato growth indicator after ten consecutive days of application of pretreated ZSM-5 molecular sieves and pretreated control material in a facility cultivation environment, A being the stem thickening rate, B being the fresh weight gain, C being the growth phenotype of the ` Condine Red ` tomato seedling at day 10, D being a partial enlargement of C; a. b represents significant differences at the 5% level between the different treatments.
Detailed Description
Example 1: improvement of CO in closed environment by ZSM-5 molecular sieve2Concentration of
Pretreating a ZSM-5 molecular sieve: adding 5cm into a 12.5L sealed box3ZSM of5 molecular sieve, then filling the sealed box with CO2And sealing and standing for 0.1h, 0.5h, 1h, 2h, 4h, 8h and 12h respectively. Comparative material CaCO3The pretreatment step was performed with the same parameters.
Respectively and rapidly transferring the pretreated ZSM-5 molecular sieve and the control material to CO2Standing slow-release CO in 56L air-tight box with initial concentration of 480ppm2And after 0.5h, detecting and recording CO in a 56L air-tight box2The change in concentration. The results are shown in FIG. 1, where both the pretreated ZSM-5 molecular sieve and the control material allowed the CO in the empty sealed box2The concentration is increased, but the ZSM-5 molecular sieve makes CO in an empty sealed box2The concentration is increased by 380-480 ppm, and the control material enables CO in the air-tight box2The concentration is increased by 50-120 ppm, and the concentration of CO in the ZSM-5 molecular sieve after being pretreated for 12 hours2The enrichment effect is stronger than that of pretreatment for 0.1h and 0.5h, and is not much different from that of pretreatment for 1h, 4h or 8 h.
Example 2: recycling of ZSM-5 molecular sieve
Pretreating a ZSM-5 molecular sieve: adding 5cm into a 12.5L sealed box3ZSM-5 molecular sieve, then filling the sealed box with CO2And sealing and standing for 4 hours. Comparative material CaCO3The pretreatment step was performed with the same parameters.
Respectively and rapidly transferring the pretreated ZSM-5 molecular sieve and the control material to CO2Standing in a 56L air-tight box with initial concentration of 480ppm for releasing CO slowly2Detecting and recording CO in 56L of empty sealed box within 40min2The change in concentration.
And after 3 hours, taking out the ZSM-5 molecular sieve and the contrast material, carrying out the steps of pretreatment and release again according to the parameters, and repeating for 1-10 times. Testing the reuse times of the ZSM-5 molecular sieve and the reference material CO2The effect of the enrichment effect is shown in FIG. 2, in which the ZSM-5 molecular sieve used repeatedly for 10 times and the ZSM-5 molecular sieve used for the first time are used repeatedly for CO2The enrichment effect has no obvious difference.
Example 3: application of pretreated ZSM-5 molecular sieve to CO in facility cultivation environment2Concentration, photosynthesis of crops, and influence of crop growth
Pretreating a ZSM-5 molecular sieve: adding 25cm into a 12.5L sealed box3ZSM-5 molecular sieve, then filling the sealed box with CO2And sealing and standing for 1 h. Comparative material CaCO3The pretreatment step was performed with the same parameters.
The pretreated ZSM-5 molecular sieve and the reference material are quickly transferred to CO2Standing for slowly releasing CO in plant facility cultivation environment with concentration reduced to 400ppm2Detecting and recording CO in plant facility cultivation environment2And (5) taking out the ZSM-5 molecular sieve after 5 hours.
The plant facility cultivation environment is 580L sealed incubator containing 8 'Condine Red' tomato seedlings with growing vigor and consistent seedling age, photoperiod is 8:00-20:00, light intensity is 200-300 μmol/m2/s1。
Applying the pretreated ZSM-5 molecular sieve or the control material for 1h, and passing through CO2Recorder detects real-time CO in plant facility cultivation environment2Concentration value: the ZSM-5 zeolite group was 550. + -.50 ppm, and the control material group was 400. + -.50 ppm (FIG. 3). Setting parameters of a photosynthetic instrument as parameters in a plant facility cultivation environment, and measuring functional intercellular CO of the first fully-unfolded leaf of the 'Condition Red' tomato seedling from top to bottom2Concentration and net photosynthetic Rate results are shown in FIGS. 4A and 4B, respectively, for ` Condine Red ` tomato seedling leaf intercellular CO in the ZSM-5 molecular sieve group as compared to the control material group2The concentration is improved by 34 percent, and the net photosynthetic rate is improved by 8.7 percent.
The pretreatment-release steps are continuously repeated for ten days under the same conditions, the ZSM-5 molecular sieve is repeatedly utilized, and the molecular sieve is dried and regenerated at high temperature for continuous use after 3 times of repeated utilization, wherein the high-temperature drying and regeneration conditions are 200 ℃ and 12 hours. The change of plant growth indicator after ZSM-5 molecular sieve group and control material group treatment was measured (FIG. 5). The stem thickness of 1cm at the upper part of cotyledon of the 'compressor Red' tomato plant on 0 th and 10 th days is measured by using a vernier caliper, and the stem thickness increment of the ZSM-5 molecular sieve group and the stem thickness increment of the control material group are calculated, so that the result is shown in figure 5A, and compared with the control material group, the stem thickness increment of the 'compressor Red' tomato plant in the ZSM-5 molecular sieve group is increased by 76%.
The fresh weight of the whole plant of the 'cond Red' tomato plant on the 0 th and 10 th days was measured by an analytical balance, and the fresh weight gains of the ZSM-5 molecular sieve group and the control material group were calculated, and the results are shown in FIG. 5B, in which the fresh weight gain of the 'cond Red' tomato plant in the ZSM-5 molecular sieve group was increased by 62.5% as compared with the control material group.
Fig. 5C is a picture of the growth phenotype of the 'conditioner Red' tomato seedlings at day 10, and fig. 5D is a partial enlargement of fig. 5C.
Example 4: application of pretreated ZSM-5 molecular sieve to CO in facility cultivation environment2Influence of concentration
Pretreating a ZSM-5 molecular sieve: adding 50cm into a 12.5L sealed box3ZSM-5 molecular sieve, then filling the sealed box with CO2And sealing and standing for 1 h. Comparative material CaCO3The pretreatment step was performed with the same parameters.
The pretreated ZSM-5 molecular sieve and the reference material are quickly transferred to CO2Standing for slowly releasing CO in plant facility cultivation environment with concentration reduced to 400ppm2Detecting and recording CO in plant facility cultivation environment2The change in concentration.
The plant facility cultivation environment is 580L sealed incubator containing 8 'Condine Red' tomato seedlings with growing vigor and consistent seedling age, photoperiod is 8:00-20:00, light intensity is 200-300 μmol/m2/s1。
Applying the pretreated ZSM-5 molecular sieve or the control material for 1h, and passing through CO2Recorder detects real-time CO in plant facility cultivation environment2Concentration value: the application amount of the ZSM-5 molecular sieve is increased (compared with example 3) after the ZSM-5 molecular sieve group is 620 plus or minus 50ppm and the control material group is 500 plus or minus 50ppm (figure 3), so that the application amount of the ZSM-5 molecular sieve is increased to CO in a plant cultivation facility2The effect of enrichment.
Claims (3)
1. Facility CO for improving plant cultivation by applying ZSM-5 molecular sieve2A method of concentration and crop growth comprising the steps of:
(1) pretreating the ZSM-5 molecular sieve to make the molecular sieve fully adsorb CO2；
(2) Transferring the pretreated ZSM-5 molecular sieve to CO2In the facility cultivation environment with the concentration less than or equal to 480ppm, the ZSM-5 molecular sieve is kept stand to slowly release CO2(ii) a CO improving facility cultivation environment2Concentration, promoting the growth of crops;
the pretreatment mode is as follows: filling CO into the closed space filled with ZSM-5 molecular sieve2Sealing and standing for 1-4 h; the ZSM-5 molecular sieve and CO2The volume ratio of the filling amount is 0.1-4: 1000;
in the step (2), the dosage of the ZSM-5 molecular sieve is 40-90 cm per cubic meter of facility cultivation environment3；
In the step (2), the ZSM-5 molecular sieve stands to release CO slowly2Taking out after at least 3h, returning to the step (1), and repeating for 1-10 times;
the method can require CO under normal temperature and pressure2Enriched facility cultivation environment application of CO2And (4) air fertilizer.
2. The enhancement of plant cultivation facility CO by application of ZSM-5 molecular sieves of claim 12The method for concentration and crop growth is characterized in that the ZSM-5 molecular sieve is dried and regenerated at high temperature after being reused for 3 times and then is continuously used, and the high-temperature drying and regeneration conditions are 100-300 ℃ and 1-48 hours.
3. Enhancement of plant cultivation facility CO by application of ZSM-5 molecular sieves according to claim 12A method for controlling the concentration and growth of a crop, characterized in that said crop is a tomato.
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